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United States Patent |
5,322,882
|
Okamoto
|
June 21, 1994
|
Polycarbonate/polyorganosiloxane composition
Abstract
A polycarbonate-based resin composition excelling in not only impact
resistance but also other physical properties comprises 6 to 90% by weight
of a polycarbonate/polyorganosiloxane copolymer, 10 to 60% by weight cf
glass fibers and 0 to 84% by weight of a polycarbonate resin. The amount
of the polyorganosiloxane contained in the resin components is in a range
of 0.5 to 40% by weight.
Inventors:
|
Okamoto; Masaya (Ichihara, JP)
|
Assignee:
|
Idemitsu Petrochemical Co., Ltd. (Tokyo, JP)
|
Appl. No.:
|
006177 |
Filed:
|
January 15, 1993 |
Foreign Application Priority Data
| Dec 26, 1988[JP] | 63-326349 |
Current U.S. Class: |
524/537; 524/588; 525/462; 525/464; 525/474 |
Intern'l Class: |
C08L 069/00; C08L 051/00 |
Field of Search: |
524/537,588
525/462,464,474
|
References Cited
U.S. Patent Documents
3419635 | Dec., 1968 | Vaughn, Jr. | 528/25.
|
3640943 | Feb., 1972 | Bostick et al. | 260/375.
|
4126740 | Nov., 1978 | Factor et al. | 528/29.
|
4147707 | Apr., 1979 | Alewelt et al. | 524/611.
|
4161469 | Jul., 1979 | LeGrand et al. | 525/439.
|
4167536 | Sep., 1979 | Factor | 525/450.
|
4224215 | Sep., 1980 | Macke | 524/611.
|
4224215 | Sep., 1980 | Macke | 524/611.
|
4612238 | Sep., 1986 | Della Vecchia et al. | 428/228.
|
4616042 | Oct., 1986 | Avakian.
| |
4732949 | Mar., 1988 | Paul et al. | 525/464.
|
5037937 | Aug., 1991 | Komatsu et al.
| |
Foreign Patent Documents |
278498 | Aug., 1988 | EP.
| |
WO8000084 | Jan., 1980 | WO.
| |
WO9100885 | Jan., 1991 | WO.
| |
Primary Examiner: Michl; Paul R.
Assistant Examiner: Cain; Edward J.
Attorney, Agent or Firm: Frishauf, Holtz, Goodman & Woodward
Parent Case Text
This application is a continuation of application Ser. No. 07/443,558,
filed Nov. 29, 1989 now abandoned.
Claims
What is claimed is:
1. A polycarbonate-based resin composition comprising 10 to 80% by weight
of a polycarbonate/polyorgansiloxane copolymer having a viscosity average
molecular weight of 10,000 to 40,000 and comprising terminal t-butylphenol
groups, wherein the polycarbonate is obtained from bisphenol A, 20 to 50%
by weight of glass fibers and 0 to 70% by weight of a polycarbonate resin,
the amount of said polyorganosiloxane accounting for 3.5 to 29% by weight
of said resin components, the composition having an Izod impact strength
of more than 23 kg.multidot.cm/cm.
2. The polycarbonate-based resin composition as claimed in claim 1, wherein
the polycarbonate/polyorganosiloxane copolymer is comprised of a
polycarbonate segment having repeating units expressed by the following
formula I;
##STR4##
wherein: Z is single bone, an ether bond, an alkylene group having 1 to 8
carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a
cycloalkylene group having 5 to 15 carbon atoms, a cyclo-alkylidene group
having 5 to 15 carbon atoms, a sulfonyl group, a sulfoxide group, a
carbonyl group, a sulfide group or a group:
##STR5##
R.sup.1 and R.sup.2, which may be identical with or different from each
other, each stand for a hydrogen atom, a halogen atom or an alkyl group
having 1 to 8 carbon atoms,
m and n each stand for an interger of 1 to 4, provided that when m is 2 or
more, R.sup.1 may be identical or different and when n is 2 or more,
R.sup.2 may be identical or different, and
l is between 3 and 50, and a polyorganosiloxane segment having repeating
units expressed by the following formula II;
##STR6##
wherein: R.sup.3, R.sup.4 and R.sup.5, which may be identical with or
different from one another, each stand for a hydrogen atom, a alkyl group
having 1 to 6 carbon atoms or a phenyl group, and
p a q each are an interger of 1 or more.
3. The polycarbonate=based resin composition as claimed in claim 1, wherein
the amount of the polycarbonate/poly-organosiloxane copolymer is 15 to 80%
by weight.
4. The polycarbonate-based resin composition as claimed in claim 1, wherein
the glass fiber is surface-treated.
5. The polycarbonate-based resin as claimed in claim 1, wherein the
composition comprises a polycarbonate having a viscosity-average molecular
weight of 10,000 to 100,000.
6. The polycarbonate-based resin composition as claimed in claim 1, wherein
the polycarbonate/polyorganosiloxane copolymer has a viscosity-average
molecular weight of 15,000 to 35,000.
7. The polycarbonate-based resin composition as claimed in claim 1, wherein
the glass fibers are 1 to 8 mm in length and 3 to 20 .mu.m in diameter.
8. The polycarbonate-based resin composition as claimed in claim 6, wherein
the glass fibers are 3 to 6 mm in length and 5 to 15 .mu.m in diameter.
9. The polycarbonate-based resin composition as claimed in claim 8, wherein
the composition comprises a polycarbonate resin having a viscosity-average
molecular weight of 20,000 to 40,000.
10. The polycarbonate-based resin composition as claimed in claim 2,
wherein the amount of the polycarbonate/polyarganosiloxane copolymer is 15
to 80% by weight; the glass fibers are surface treated, and have a length
of 1 to 8 mm and a diameter of 3 to 20 .mu.m; the composition comprises a
polycarbonate resin having a viscosity-average molecular weight of 10,000
to 100,000 resin ; and the polycarbonate/polyorganosiloxane copolymer has
a viscosity-average molecular weight of 15,000 to 35,000.
11. The polycarbonate-based resin composition as claimed in claim 10,
wherein the glass fibers have a length of 3 to 6 mm and a diameter of 5 to
15 .mu.m; and the composition comprises a polycarbonate resin having a
viscosity-average molecular weight of 20,000 to 40,000.
12. The polycarbonate-based resin composition as claimed in claim 1,
wherein said polycarbonate resin is in an amount of 10 to 70% by weight.
13. The polycarbonate-based resin composition as claimed in claim 1,
wherein the polyorganosiloxane content is 10% by weight.
14. The polycarbonate-based resin composition as claimed in claim 2,
wherein the polyorganosiloxane segment has a degree of polymerization of 5
to 300.
15. The polycarbonate-based resin composition as claimed in claim 12,
wherein the polycarbonate/polyorganosiloxane copolymer is comprised of
a polycarbonate segment having repeating units expressed by the following
formula I:
##STR7##
wherein Z is single bond, an ether bond, a alkylene group having 1 to 8
carbon atoms, an alkylidened group having 2 to 8 carbon atoms, a
cylcoalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group
having 5 to 15 carbon atoms, a sulfonyl group, a fulfoxide group, a
carbonyl group, a sulfide group or a group of the following formula:
##STR8##
R.sup.1 and R.sup.2, which are identical with or different from each
other, each is a hydrogen atom, a halogen atom or an alkyl group having 1
to 8 carbon atoms,
m and n each is an integer of 1 to 4 , provided that when m is 2 or more,
R.sup.1 is identical or different and when n is 2 or more, R.sup.2 is
identical or different, and
l is between 3 and 50, and
a polyorganosiloxane segment having repeating units expressed by the
following formula II:
##STR9##
wherein R.sup.3, R.sup.4 and R.sup.5, which are identical with or
different from one another, each is a hydrogen atom, a alkyl group having
1 to 6 carbon atoms or a phenyl group, and
p and q each is an integer of 1 or more.
16. The polycarbonate-based resin composition as claimed in claim 15,
wherein the amount of the polycarbonate/polyorganosiloxane copolymer is 15
to 80% by weight; the glass fibers are surface treated and have a length
of 1 to 8 mm and a diameter of 3 to 20 .mu.m; the composition comprises a
polycarbonate resin having a viscosity-average molecular weight of 10,000
to 100,000 and the polycarbonate/polyorganosiloxane copolymer has a
viscosity-average molecular weight of 15,000 to 35,000
17. The polycarbonate-based resin composition as claimed in claim 16,
wherein the glass fibers have a length of 3 to 6 mm and a diameter of 5 to
15 .mu.m; and the composition comprises a polycarbonate resin having a
viscosity-average molecular weight of 20,000 to 40,000.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polycarbonate-based resin composition
and, more particularly, to a glass fiber-reinforced polycarbonate-based
resin composition excelling specially in impact resistance and is suitable
for use in various industrial materials.
Prior Art
Polycarbonate resins excel in mechanical strength, electrical
characteristics, transparency, etc., and find various applications in the
form of engineering plastics.
Additionally, there is known a glass fiber-reinforced polycarbonate resin
in which glass fibers are incorporated into a polycarbonate resin to
improve its rigidity and dimensional stability.
However, the addition of glass fibers tends to give rise to a drop of Izod
impact strength due to brittle fracture. For that reason, compositions
comprising such glass fiber-reinforced polycarbonate resins and further
including an organo-polysiloxane have been proposed (see Japanese Patent
Publication No. 35929/1984 and Japanese Patent Laid-Open (Kokai)
Publication No. 501860/1982).
A problem with molded or otherwise shaped articles obtained from such
compositions is, however, that they are poor in insulating properties.
With that problem in mind, compositions of glass fiber-reinforced
polycarbonate resins containing a small amount of
organopolysiloxane/polycarbonate copolymers have been proposed (see
Japanese Patent Kokai Publication No. 160052/1980).
While such compositions are improved in terms of impact resistance to some
extent, their impact resistance is still not enough to find use in fields
for which especially high impact resistance is needed, for instance,
chassis or electrically powered tool fields.
SUMMARY OF THE INVENTION
As a result of extensive and intensive studies made to provide a solution
to the above problems, it has been found that a polycarbonate-based resin
composition excelling in not only impact resistance but also rigidity,
dimensional stability, etc. can be obtained by using a
polycarbonate/polyorganosiloxane copolymer, glass fibers and a
polycarbonate resin at a specific proportion. Such findings underlie the
present invention.
More specifically, the present invention provides a polycarbonate-based
resin composition, characterized by comprising 6 to 90% by weight of a
polycarbonate/polyorganosiloxane copolymer, 10 to 60% by weight of glass
fibers and 0 to 84% by weight of a polycarbonate resin, and in that the
amount of said polyorganosiloxane accounts for 0.5 to 40% by weight of the
resin components.
DETAILED DESCRIPTION OF THE INVENTION
The polycarbonate/polyorganosiloxane copolymer used in the present
invention is comprised of a polycarbonate segment having repeating units
expressed by the following formula I:
##STR1##
wherein:
Z is single bond, ether bond, alkylene group having 1 to 8 carbon atoms, an
alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having
5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms,
a sulfonyl group, a sulfoxide group, a carbonyl group, sulfide group or a
group:
##STR2##
R.sup.1 and R.sup.2, which may be identical with or different from each
other, each stand for a hydrogen atom, a halogen atom or an alkyl group
having 1 to 8 carbon atoms,
m and n each stand for an interger of 1 to 4, provided that when m is 2 or
more, R.sup.1 may be identical or different and when n is 2 more, R.sup.2
may be identical or different, and
l is between 3 and 50, and a polyorganosiloxane segment having repeating
units expressed by the following formula II:
##STR3##
wherein:
R.sup.3, R.sup.4 and R.sup.5, which may be identical with or different from
one another, each stand for a hydrogen atom, an alkyl group having 1 to 6
carbon atoms or a phenyl group, and
p and q each are an interger of 1 or more. Usually, the polyorganosiloxane
segment has a degree of polymerization of 5 to 300.
The above polycarbonate/polyorganosiloxane copolymer is a block copolymer
comprising the polycarbonate segment having repeating units expressed by
the general formula I and the polyorganosiloxane segment having repeating
units expressed by the general formula II, and has a viscosity-average
molecular weight of 10,000 to 40,000, preferably 15,000 to 35,000.
For instance, such a polycarbonate/polyorganosiloxane copolymer may be
prepared by dissolving a pre-prepared polycarbonate oligomer forming the
polycarbonate segment and a polyorganosiloxane having a terminal reactive
group and forming the polyorganosiloxane segment in a solvent such as
methylene chloride, chlorobenzene or pyridine, adding an aqueous sodium
hydroxide solution of bisphenol to the resulting solution and subjecting
that solution to an interface reaction with a catalyst such as
triethylamine or trimethylbenzyl-ammonium chloride. Use may also be made
of polycarbonate/polyorganosiloxane copolymers prepared by such methods as
set forth in Japanese Patent Publication Nos. 30108/1969 and 20510/1970.
The polycarbonate having repeating units expressed by the general formula I
may be prepared by a solvent method in which a divalent phenol is allowed
to react with a carbonate precursor such as phosgene or subjected to an
ester exchange reaction with a carbonate precursor such as diphenyl
carbonate in a solvent such as methylene chloride in the presence of an
acid acceptor and a molecular-weight regulator, both known in the art.
The divalent phenols preferably used in the present invention include
bisphenols. Particular preference is given to 2,2-bis(4-hydroxyphenyl)
propane (bisphenol A). The bisphenol A may be partly or wholly substituted
by other divalent phenols. As the divalent phenols other than the
bisphenol A, reference may be made to compounds such as, for instance,
(4-hydroxyphenyl) alkanes, hydroquinone, 4,4'-dihydroxy-diphenyl,
bis(4-hydroxy-phenyl) cycloalkanes, bis(4-hydroxyphenyl) sulfide,
bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide,
bis(4-hydroxyphenyl) ether and bis(4-hydroxyphenyl) ketone or halogenated
bisphenols such as bis(3,5-dibromo-4-hydroxyphenyl) propane and bis
(3,5-dichloro-4-hydroxyphenyl) propane.
The polycarbonate may be a homopolymer (oligomer) with one of such divalent
phenols or a copolymer with two or more thereof. Alternatively, it may be
a thermoplastic branched polycarbonate obtained by using the above
divalent phenols in combination with a polyfunctional aromatic compound.
For instance, the polyorganosiloxane expressed by the general formula II
may be obtained by the reaction of a dialkyldichlorosilane and/or
diaryldichlorosilane with water. The monomer of such a polyorganosiloxane
may include dimethylsiloxane or methylphenylsiloxane.
Such a polycarbonate/polyorganosiloxane copolymer as mentioned above is
incorporated into the composition at a proportion of 6 to 90% by weight,
preferably 15 to 80% by weight. If the quantity of said copolymer is less
than 6% by weight, there is then no improvement in impact resistance. In a
quantity higher than 90% by weight, on the other hand, there is a drop of
dimensional stability.
The quantity of the polyorganosiloxane contained in the resin except the
glassy component (a total quantity of the polycarbonate/polyorganosiloxane
copolymer + the polycarbonate resin) is 0.5 to 40% by weight, preferably
1.0 to 35% by weight. If the quantity of the polyorganosiloxane is below
0.5% by weight, there is then no improvement in impact resistance. In a
quantity exceeding 40% by weight, on the other hand, any copolymer having
sufficient molecular weight cannot be obtained.
Referring then to the glass fibers used in the present invention, any one
of alkali-containing glass, low-alkali glass and non-alkali glass may be
used to this end. Preferably, the glass fibers used are 1 to 8 mm,
particularly 3 to 6 mm in length and 3 to 20 .mu.m, particularly 5 to 15
.mu.m in diameter. The glass fibers may be used in any nonrestrictive
forms such as rovings, milled fibers and chopped strands, and may be used
alone or in combination of two or more.
As such glass fibers, use may also be made of those surface-treated with
silane coupling agents such as aminosilanes, epoxy-silanes, vinylsilanes
or methacrylsilanes, or chromium complex compounds, boron compounds or
like other compounds to improve their affinity with respect to the
polycarbonate/polyorgano-siloxane copolymers and polycarbonate resins.
Such glass fibers as mentioned above are incorporated into the composition
at a proportion of 10 to 60% by weight, preferably 15 to 55% by weight. A
proportion of the glass fibers less than 10% by weight is unpreferred,
since there is then a drop of dimensional stability. A proportion of the
glass fibers exceeding 60% by weight is again unpreferred, since kneading
is unfeasible.
According to the present invention, a polycarbonate resin may be used, if
required.
The polycarbonate resin has repeating units expressed by the general
formula I and, as mentioned above, may be easily obtained by the reaction
of a divalent phenol with phosgene by way of example. The divalent phenols
used may include such phenols as already mentioned.
The polycarbonate resin used in the present invention has a
viscosity-average molecular weight of preferably 10,000 to 100,000, most
preferably 20,000 to 40,000.
The polycarbonate resin is incorporated into the composition at a
proportion of 0 to 84% by weight, preferably 0 to 70% by weight. If the
proportion of the polycarbonate resin exceeds 84% by weight, there is then
no improvement in impact resistance.
The polycarbonate-based resin composition according to the present
invention is essentially comprised of the above
poly-carbonate/polyorganosiloxane copolymer, glass fibers and
poly-carbonate resin, and may additionally contain any various additives,
if required, provided that the object of the present invention is
achievable. For instance, carbon fibers, metal fibers, inorganic fillers,
metal powders, UV absorbers, flame retardants, colorants, etc. may be
added.
The polycarbonate-based resin composition according to the present
invention may be obtained by blending and kneading the above components
together To this end, blending and kneading may be carried out in
conventional manners with, for instance, ribbon blenders, Henschel mixers,
Banbury mixers, drum tumblers, single-, twin- or multi-screw extruders,
Ko-kneaders or like other equipment. For kneading, a heating temperature
of 250 to 300.degree. C. is usually applied.
The polycarbonate-based resin composition according to the present
invention excels in not only impact resistance but also rigidity expressed
in terms of bending strength and tensile modulus of elasticity or
dimensional stability.
Thus, the present compositions are effectively used in various industrial
fields inclusive of electric/electronic fields, in particular fields for
which high impact resistance is needed, e.g., chassis, or similar other
fields
EXAMPLES
The present invention will now be explained in more detail with reference
to the following examples.
PREPARATION EXAMPLE 1--
Preparation of reactive Polykimethyl-Siloxane
Over two hours, a mixture of 100 g of water with 206 g of dioxane was added
to 800 g of dimethyldichlorosilane. Under mild reflux, the resulting
mixture was heated, while stirred, into a homogeneous state. The mixture
was stripped in vacuo and brought up to 202.degree. C. at a pressure 12
mmHg. Then, the stripped product was filtrated to obtain a transparent
oily product. Dissolved in 130 g of dry dichloromethane were 225 g of such
an oily product, and the solution was added under intensive agitation to a
mixture of 114 g of bisphenol A, 130 g of dry pyridine and 1300 g of
dichloromethane over 65 minutes. Afterwards, the product was alkali-washed
with 1000 g of an aqueous solution of sodium hydroxide (0.01N), then
acid-washed with 1000 g of hydrochloric acid (0.1 N) and finally washed
with 1000 g of water. Removal of dichloromethane by evaporation gave the
end reactive polydimethylsiloxane (reactive PDMS for short) having a
terminal phenolic hydroxyl group.
PREPARATION EXAMPLE 1--2
Preparation of reactive PDMS
In Preparation Example 1--1, the amount of the first mentioned water was
changed from 100 g to 140 g. Under otherwise similar conditions, the
reactive PDMS was obtained.
PREPARATION EXAMPLE 1--3
Preparation of Reactive PDMS
As the reactive PDMS, use was made of silicone oil reactive at both
terminals (KF 6002, Shinetsu Silicone Co., Ltd.).
PREPARATION EXAMPLE 1-4
Preparation of Reactive PDMS
Mixed together were 1483 g of octamethylcyclotetrasiloxane, 137 g of
1,1,3,3-tetramethyldisiloxate and 35 g of 86% sulfuric acid, and the
mixture was stirred at room temperature for 17 hours. Afterwards, an oily
phase was separated, and 25 g of sodium hydrogencarbonate were added
thereto, followed by one hour stirring. After filtration, the product was
distilled in vacuo at 150.degree. C. and 3 mmHg to remove low-boiling
matters.
Added to a mixture of 60 g of 2-allylphenol with 0.0014 g of platinum in
the form of a platinum/alcoholate complex were 294 g of the above-obtained
oil at a temperature of 90.degree. C. The mixture was stirred for 3 hours,
while maintained at a temperature of 90.degree. C. to 115.degree. C. The
product was extracted wi chloride and washed with three portions of 80%
aqueous methanol to remove excessive 2-allylphenol. The product was dried
over anhydrous sodium sulfate and rid of the solvents in vacuo at a
temperature of up to 115.degree. C. to obtain the reactive PDMS.
PREPARATION EXAMPLE 1-5
Preparation of Reactive PDMS
As the reactive PDMS, use was made of silicone oil reactive at both
terminals (X-22-165B, Shinetsu Silicone Co., Ltd.).
PREPARATION EXAMPLE 1-6
Preparation of Reactive PDMS
As the reactive PDMS, use was made of silicone oil reactive at both
terminals (X-22-165C , Shientsu Silicone Co., Ltd.).
PREPARATION EXAMPLE 2
Preparation of Polycarbonate Oligomer
Sixty (60) kg of bisphenol A were dissolved in 400 liters of a 5% aqueous
solution of sodium hydroxide to prepare an aqueous solution of bisphenol A
in sodium hydroxide. Then, the solution was maintained at room
temperature. The aqueous sodium hydroxide solution of bisphenol A and
methylene chloride were introduced at the respective flow rates of 138
liters per hour and 69 liters per hour into a tubular reactor of 10 mm in
inner diameter and 10 m in length through an orifice plate, into which
10.7 kg/hour of phosgene were blown in cocurrent relation thereto, for
three-hour continuous reactions. The tubular reactor used was of a double
structure designed to pass cooling water through an outer jacket to keep
the discharge temperature of the reaction solution at 25.degree. C. The
discharge solution was also regulated to pH 10-11. The thus obtained
reaction solution was allowed to stand to separate and remove an aqueous
phase, thereby obtaining a methylene chloride phase (220 liters), to which
170 liters of methylene chloride were added under sufficient agitation to
obtain a polycarbonate oligomer (with a concentration of 317 g/liters).
This polycarbonate oligomer (PC oligomer for short) was found to have a
degree of polymerization of 3-4.
PREPARATION EXAMPLE 3-1
Preparation of PC-PDMS Copolymer A
Dissolved in 2 liters of methylene chloride were 160 g of the reactive PDMS
obtained in Preparation Example 1--1, and the solution was mixed with 10
liters of the PC oligomer obtained in Preparation Example 2. Added to the
mixture were 26 g of sodium hydroxide dissolved in 1 liter of water and
5.7 cc of triethylamine, followed by one-hour stirring at 500 rpm and room
temperature. Afterwards, 600 g of bisphenol A dissolved in 5 liters of an
aqueous solution of 5.2% by weight sodium hydroxide, 8 liters of methylene
chloride and 81 g of p-tert.-butylphenol were added to the solution,
followed by two-hour stirring at 500 rpm and room temperature. Thereafter,
an additional 5 liters of methylene chloride were added to the solution,
and the resulting product was washed with 5 liters of water, then
alkali-washed with 5 liters of a 0.01 N aqueous solution of sodium
hydroxide, then acid-washed with 5 liters of 0.1 N hydrochloric acid and
finally washed with 5 liters of water. Subsequent removal of methylene
chloride gave a PC-PDMS copolymer A in the form of chips, which found to
have a PDMS content of 3.5% by weight.
PREPARATION EXAMPLE 3-2
Preparation of PC-PDMS Copolymer
In Preparation Example 3-1, 500 g of the reactive PDMS obtained in
Preparation Example 1-2 were used in place of 160 g of the reactive PDMS
obtained in Preparation Example 1--1. Under otherwise similar conditions
as in Preparation Example 3-1, a PC-PDMS copolymer B was prepared, which
was found to have a PDMS content of 10% by weight.
PREPARATION EXAMPLE 3--3
Preparation of PC-PDMS Copolymer
In Preparation Example 3-1, 2.6 kg of the reactive PDMS obtained in
Preparation Example 1-2 were used in place of 160 g of the reactive PDMS
obtained in Preparation Example 1--1 and the amount of sodium hydroxide
used was changed from 26 g to 50 g. Under otherwise similar conditions as
in Preparation Example 3-1, a PC-PDMS copolymer C was prepared, which was
found to have a PDMS content of 29% by weight.
PREPARATION EXAMPLE 3-4
Preparation of PC-PDMS Copolymer D
Dissolved in 9.5 liters of the PC oligomer obtained in Preparation Example
2 were 480 g of the reactive PDMS obtained in Preparation Example 1-3
(silicone oil reactive at both terminals), and 101 g of triethylamine were
slowly added dropwise to the solution under agitation. After the dropwise
addition, the solution was stirred for 1 hour and then acid-washed with 5
liters of 0.1 N hydrochloric acid to separate an organic phase.
Thereafter, added to the solution were 600 g of bisphenol A dissolved in 5
liters of an aqueous solution of 5.2% by weight sodium hydroxide, 8 liters
of methylene chloride and 25 g of p-tert.-butylphenol, followed by
two-hour stirring at 500 rpm and room temperature. After that, additional
5 liters of methylene chloride were added to the solution, which was in
turn washed with 5 liters of water, then alkali-washed with 5 liters of a
0.01 N aqueous solution of sodium hydroxide, then acid-washed with 5
liters of 0.1 N hydrochloric acid and finally washed with 5 liters of
water. Subsequent removal of methylene chloride gave a PC-PDMS copolymer D
in the form of chips, which was found to have a PDMS content of 3.9% by
weight.
PREPARATION EXAMPLE 3-5
Preparation of PC-PDMS Copolymer E
As the PC-PDMS copolymer, use was made of Macrolon Type 1207produced by
Bayer Corp., which had a PDMS content of 4.8% by weight.
It is understood that the PDMS contents of the above PC-PDMS copolymers
were all determined by H NMR.
PREPARATION EXAMPLE 3-6
Preparation of PC=PDMS Copolymer F
In Preparation Example 3-1, the reactive PDMS obtained in Preparation
Example 1-4 was used in place of the reactive PDMS obtained in Preparation
Example 1--1. Under otherwise similar conditions as in Preparation Example
3--1, a PC-PDMS copolymer F was obtained, which was found to have a PDMS
content of 3.5% by weight.
PREPARATION EXAMPLE 3-7
Preparation of PC-PDMS Copolymer G
In Preparation Example 3-1, the reactive PDMS obtained in Preparation
Example 1-5 was used in place of the reactive PDMS obtained in Preparation
Example 1--1. Under otherwise similar conditions as in Preparation Example
3-1, a PC-PDMS copolymer G was obtained, which was found to have a PDMS
content of 3.5% by weight.
PREPARATION EXAMPLE 3-8
Preparation of PC-PDMS Copolymer H
In Preparation Example 3-1, the reactive PDMS obtained in Preparation
Example 1-6 was used in place of the reactive PDMS obtained in Preparation
Example 1--1. Under otherwise similar conditions as in Preparation Example
3-1, a PC-PDMS copolymer H was obtained, which was found to have a PDMS
content of 3.5% by weight.
EXAMPLES 1-18 AND COMPARATIVE EXAMPLES 1-5
The PC-PDMS copolymers A-H obtained in Preparation Examples 3-1 to 3-8,
polycarbonate (having an average molecular weight of 25,000; and available
under the trade name of Toughron A-2500, produced by Idemitsu
Petrochemical Co., Ltd.) and glass fibers (non-alkali glass
surface-treated with aminosilane; and 6 mm in length and 13 .mu.m in
diameter) were blended together at the proportions specified in Table 1,
and the blends were formed through a 30-mm vented extruder into pellets,
which were in turn injection-molded at a temperature of 300.degree. C. to
obtain molded samples for the determination of their physical properties.
The results are set forth in Table 1. It is understood that the glass
fibers were supplied downstream of the hopper of the extruder through
which the resin stock was fed in.
TABLE 1
__________________________________________________________________________
PDMS Content
PC-PDMS Copolymer of Resin Izod Impact
Tensile
Bending
Amount Polycarbonate
Components
Glass fibers
Strength*.sup.1
Modulus*.sup.2
Strength*.sup.3
Types
(weight %)
(weight %)
(weight %)
(weight %)
(kg .multidot. cm/cm)
(kg/cm.sup.2)
(kg/cm.sup.2)
__________________________________________________________________________
Example 1
A 50 0 3.5 50 31 84800 2400
Example 2
A 70 0 3.5 30 27 58900 1800
Example 3
A 90 0 3.5 10 20 33500 1200
Example 4
B 70 0 10 30 28 59000 1800
Example 5
C 50 0 29 50 30 85200 2300
Example 6
C 70 0 29 30 30 59000 1700
Example 7
C 90 0 29 10 21 33600 1100
Example 8
D 70 0 3.9 30 29 59100 1800
Example 9
A 30 60 1.2 10 20 33700 1200
Comparative
-- 0 90 0 10 11 33700 1200
Example 1
Example 10
C 10 70 3.6 20 23 46300 1600
Comparative
-- 0 80 0 20 15 46500 1600
Example 2
Example 11
B 20 50 2.9 30 28 59000 1800
Example 12
B 40 30 5.7 30 27 59200 1800
Example 13
B 60 10 8.6 30 27 58900 1700
Example 14
C 10 60 4.1 30 28 59000 1800
Comparative
C 5 65 2.1 30 18 58900 1700
Example 3
Comparative
-- 0 70 0 30 18 59000 1800
Example 4
Comparative
-- 0 50 0 50 19 85000 2400
Example 5
Example 15
E 70 0 4.8 30 27 58900 1700
Example 16
F 70 0 3.5 30 21 58800 1700
Example 17
G 70 0 3.5 30 22 58900 1800
Example 18
H 70 0 3.5 30 23 58800 1700
__________________________________________________________________________
*.sup.1 Measured according to JISK-7110
*.sup.2 Measured according to JISK-7113
*.sup.3 Measured according to JISK-7203
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